Three-dimensional article and method of making the same

ABSTRACT

Three-dimensional polymeric article ( 100 ) having first ( 101 ) and second ( 102 ) opposed major surfaces, a base body ( 103 ) having a first dimension, a second dimension perpendicular to the first dimension, and a thickness, wherein the thickness is orthogonal to the first and second dimensions, wherein the base body ( 103 ) comprises a plurality of alternating, adjacent first ( 107 ) and second ( 108 ) polymeric regions along the first dimension, wherein the second dimensions of the first ( 107 ) and second ( 108 ) regions extend at least partially across the second dimensions, wherein the first regions ( 107 ) have a first crosslink density, wherein the second regions ( 108 ) have a second crosslink density, wherein the second crosslink density of the second regions ( 108 ) are less than the first crosslink density of the first regions ( 107 ), wherein the first and second regions extend perpendicularly in two directions from a central plane ( 115 ) in the base body ( 103 ) parallel to the first and second dimensions of the polymeric article ( 100 ), and wherein the second regions ( 108 ) extend in each of said two directions further than does the first regions ( 107 ). Embodiments of the three-dimensional polymeric article described herein are useful for providing a dual sided, textured wrapping film such that greater grip is realized both on an item wrapped by the film and the wrapped item itself.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Patent Application No. 62/271,707, filed Dec. 28, 2015, the disclosure of which is incorporated by reference herein in its entirety.

BACKGROUND

Microstructured films, with features on the micrometer scale, have been used in a variety of technologies including overhead projector films, reflective signage, and abrasive films. Common microstructure forming processes include extrusion, embossing, and lithography (e.g., photolithography). Lithographic processes often require complex optics, relatively low throughput, and multiple processing steps, including solution based processing which may generate significant amounts of liquid waste. Microreplication processes such as extrusion and hot embossing typically require expensive master pattern rolls for any given pattern, and any changes to the pattern would require the added expense of a new master to be fabricated. In addition, the patterns are limited in both feature depth and type of pattern (e.g., based on diamond turning methods). In addition, the microreplication processes generally produce materials having a base plane (sometimes referred to as the “land” area) with patterns protruding either all above or all below the base plane. Precise registration of microstructured patterns on opposing sides of a film may allow for simultaneous features both above and below the base plane, however, these processes are significantly more complex and often have additional limitations on precision of feature placement above and below the base plane. New microstructured films, and methods of making them, are desirable.

SUMMARY

In one aspect, the present disclosure describes a three-dimensional polymeric article having first and second opposed major surfaces, a base body having a first dimension, a second dimension perpendicular to the first dimension, and a thickness, wherein the thickness is orthogonal to the first and second dimensions, wherein the base body comprises a plurality of alternating, adjacent first and second polymeric regions along the first dimension, wherein the first and second regions extend at least partially across the second dimensions, wherein the first regions have a first crosslink density, wherein the second regions have a second crosslink density, wherein the second crosslink density of the second regions are less (in some embodiments, at least 1% less, 2% less, 3% less, 4% less, 5% less, 10% less, 15% less, 20% less, 25% less, 30% less, 35% less, 40% less, 45% less, 50% less, 55% less, 60% less, 65% less, 70% less, 75% less, 80% less, 85% less, 90% less, 95% less, or even 100% less) than the first crosslink density of the first regions, wherein the first and second regions extend perpendicularly in two directions from a central plane in the base body parallel to the first and second dimensions of the polymeric article, and wherein the second regions extend in each of said two directions further than does the first regions.

In another aspect, the present disclosure describes a method comprising:

providing an oriented, crosslinkable film having first and second opposed major surfaces;

irradiating (e.g., with e-beam, ultraviolet (UV), x-ray, and/or gamma radiation) through at least a portion of the first major surface of the oriented, crosslinkable film to cause at least some portions under the first major surface to be irradiated and at least partially crosslink to provide first irradiated portions, wherein there remain after said irradiating at least second portions that are less irradiated than (which include zero irradiation) the first irradiated portions, and wherein the first irradiated portions have a lower shrink ratio than the second irradiated portions; and

dimensionally relaxing (e.g., via heating and/or via removing tension) the irradiated film. It is understood that when irradiating through a major surface of the film the surface too is irradiated. In some embodiments, the method results in the three-dimensional polymeric article described herein. In some embodiments of the method, the first major surface is masked to at least reduce exposure of the radiation.

“Crosslink density” as used herein refers to the quotient of the polymer film density divided by the average molecular mass between crosslinks, M_(c), as calculated using the Flory-Rehner equation (Equation 1).

$\begin{matrix} {\frac{1}{M_{c}} = {\frac{2}{M_{n}} - {\frac{\frac{v_{s}}{V_{1}}\left( {{\ln \left( {1 - v_{2}} \right)} + v_{2} + {\chi_{1}v_{2}^{2}}} \right)}{v_{2}^{1/3} - \frac{v_{2}}{2}}.}}} & {{Equation}\mspace{14mu} 1} \end{matrix}$

wherein, M_(c)=average molecular mass between crosslinks, M_(n)=number-average molecular mass of the un-crosslinked polymer, V₁=molar volume of the solvent, ν₂=polymer volume fraction in the equilibrium swollen gel, ν_(s)=specific volume of the polymer, and χ₁=polymer-solvent interaction parameter.

“Shrink ratio” as used herein refers to the length or width of a piece of film before dimensionally relaxing divided by the respective length or width of the same piece of film after dimensionally relaxing, wherein the film is dimensionally relaxable in the length or width dimension.

“Dimensionally relaxable” as used herein refers to the property wherein at least one dimension of a material undergoes a reduction in size during the dimensional relaxation process. Dimensional relaxation processes include heating of a heat shrinkable film or releasing tension on a stretched film. The shrink ratio of a film in the length dimension may or may not be equivalent to the shrink ratio of a film in the width dimension. One way to change the shrink ratio of a film is to change the degree of crosslinking or crosslink density of the film. Irradiating oriented, crosslinkable films with suitable radiation can increase the crosslink density of a film, and subsequently decrease the shrink ratio of the irradiated portions of the film. Suitable radiation includes electron beam, UV, x-ray, and/or gamma radiation.

Embodiments of the three-dimensional polymeric article described herein are useful, for example, in providing a dual-sided, textured wrapping film such that greater grip is realized both on an item wrapped by the film and the wrapped item itself.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a side-view schematic of an exemplary three-dimensional polymeric article described herein.

FIG. 2 is a side-view schematic of another exemplary three-dimensional polymeric article.

FIG. 3A is a perspective view scanning electron digital micrograph of Example 1.

FIG. 3B is an optical image of the top view of Example 1.

FIG. 4A is a cross-sectional view scanning electron digital micrograph of Example 1.

FIG. 4B is an optical image of the cross-sectional view of Example 1.

FIG. 5A is a perspective view scanning electron digital micrograph of Example 2.

FIG. 5B is an optical image of the top view of Example 2.

FIG. 6A is a cross-sectional view scanning electron digital micrograph of Example 2.

FIG. 6B is an optical image of the cross-sectional view of Example 2.

FIG. 7A is a top view scanning electron digital micrograph of Illustrative Example A.

FIG. 7B is an optical image of the top view of Illustrative Example A.

FIG. 8A is a cross-sectional view scanning electron digital micrograph of Illustrative Example A.

FIG. 8B is an optical image of the cross-sectional view of Illustrative Example A.

FIG. 9A is a perspective view scanning electron digital micrograph of Illustrative Example B.

FIG. 9B is an optical image of the top view of Illustrative Example B.

FIG. 10A is a cross-sectional view scanning electron digital micrograph of Illustrative Example B.

FIG. 10B is an optical image of the cross-sectional view of Illustrative Example B.

DETAILED DESCRIPTION

Referring to FIG. 1, exemplary three-dimensional polymeric article 100 has first and second opposed major surfaces 101, 102, a length, a width, and base body 103 comprising plurality of alternating, adjacent first and second polymeric regions 107, 108 along the length (and/or width; shown as length). Widths of first and second regions 107, 108 extend at least partially across width. First regions 107 have a first crosslink density. Second regions 108 have a second crosslink density. The first crosslink density of the first regions are greater than the second crosslink density of the second regions. The first and second regions extend perpendicularly in two directions from central plane 115 in base body 103 parallel to the length of polymeric article 100. Second regions 108 extend in both of the two directions further than does first regions 107.

Three-dimensional polymeric articles described herein can be made, for example, by:

providing an oriented, crosslinkable film having first and second opposed major surfaces,

irradiating (e.g., with e-beam, UV, x-ray, and/or gamma radiation) through at least a portion of the first major surface of the oriented, crosslinkable film to cause at least some portions under the first major surface to be irradiated and at least partially crosslink to provide first irradiated portions, wherein there remain after said irradiating at least second portions that are less irradiated than (which include zero irradiation) the first irradiated portions, and wherein the first irradiated portions have a lower shrink ratio than the second irradiated portions; and

dimensionally relaxing (e.g., via heating, via removing tension, etc.) the irradiated film. In some embodiments, the method results in the three-dimensional polymeric article described herein. In some embodiments of the method, the first major surface is masked to at least reduce exposure of the radiation to at least portions of the first major surface.

Techniques for masking are known in the art and include the use of aperture masks as well as photomasking as used in lithographic processes. In some embodiments, maskless radiation techniques including electron beam lithography, x-ray lithography, interference lithography, direct-write digital imaging lithography, and multiphoton lithography can be used to selectively irradiate through the first major surface.

In some embodiments, the method provides the exemplary article shown in FIG. 2, exemplary three-dimensional polymeric article 200 has first and second opposed major surfaces 201, 202, a length, a width, and a plurality of alternating first and second polymeric regions 207, 208 along the length (and/or width; length as shown). The widths of the first and second regions 207, 208 extend at least partially across the width. First regions 207 are in common plane 215. Second regions 208 project outwardly from plane 215. As shown, some second regions 208 project outwardly from plane 215 in a first direction, and some second regions 208 project outwardly from plane 215 in a second direction that is generally 180 degrees from the first direction. First regions 207 have a first crosslink density. Second regions 208 have a second crosslink density. First crosslink density of the first regions 207 is less than the second crosslink density of the second regions 208. For further details on this exemplary embodiment, see co-pending application having U.S. Ser. No. 62/271,712 (Attorney Docket No. 77413US002), filed Dec. 28, 2015, the disclosure of which is incorporated herein by reference.

In general, suitable oriented, crosslinkable films possess the ability to crosslink polymer chains in the film upon irradiation (e.g., by electron beam, x-ray, UV, and/or gamma radiation) and the property of being dimensionally relaxable, where dimensionally relaxable refers to the property wherein at least one dimension of a material undergoes a reduction in size during the relaxation process. For example, elastomeric materials in a stretched state are dimensionally relaxable, wherein the relaxation process is the release of stretch or strain in the elastic material. In the case of heat shrink materials, thermal energy is supplied to the material to allow release of the orientation-induced strain in the heat shrink material. Examples of heat shrinkable materials include polyolefins, polyurethanes, polystyrenes, polyvinylchloride, poly(ethylene-vinyl acetate), fluoropolymers (e.g., polytetrafluoroethylene (PTFE), synthetic fluoroelastomer (available, for example, under the trade designation “VITON” from DuPont, Wilmington, Del.), polyvinylidenefluoride (PVDF), fluorinated ethylene propylene (FEP)), silicone rubbers, and polyacrylates. Examples of other useful polymeric substrate materials are shape memory polymers such as polyethylene terephthalate (PET), polyethyleneoxide (PEO), poly(1,4-butadien), polytetrahydrofuran, poly(2-methly-2-oxazoline), polynorbornene, block-co-polymers, and combinations thereof). Examples of elastomeric materials include natural and synthetic rubbers, fluoroelastomers, silicone elastomers, polyurethanes, and polyacrylates. Suitable oriented, crosslinkable films may be obtained from heat shrink film suppliers, including Sealed Air, Elwood Park, N J, and Clysar, Clinton, Iowa.

Ultraviolet, or “UV,” activated cross-linkers can also be used to crosslink the film to modulate dimensional relaxation. Such UV cross-linkers may include non-copolymerizable photocrosslinkers, such as benzophenones and copolymerizable photocrosslinkers such as acrylated or methacrylated benzophenones like 4-acryloxybenzophenones. Additionally, the use of multifunctional, free radical polymerizable molecules in combination with a photo-induced free radical generator (photoinitiator) may be used to form crosslinked networks under UV irradiation. Examples of multifunctional, free radical polymerizable molecules would be multifunctional acrylates such as hexanediol diacrylate or trimethylolpropane triacrylate, both available from Sartomer, Exton, Pa. Exemplary photoinitiators are available under the trade designations “IRGACURE 651” and “DAROCUR 1173,” available from BASF, Tarrytown, N.Y.

In some embodiments, the oriented, crosslinkable films have a thickness prior to dimensional relaxation in a range from 1 micrometer to 1000 micrometers (in some embodiments, in a range from 5 micrometers to 500 micrometers, 10 micrometers to 250 micrometers, or even 10 micrometers to 100 micrometers).

In some embodiments, the oriented, crosslinkable films comprise a filler material (e.g., an inorganic material). Exemplary fillers include beads, bubbles, rods, fibers or particles comprising glass (e.g., soda lime, borosilicate, etc.), ceramic (e.g., oxides of silicon, aluminum, titanium, zirconium, or combinations thereof), metal (e.g., silver, gold, copper, aluminum, zinc) or combination thereof, and/or glass-ceramics.

The polymeric substrate having the irradiated portions thereon can be dimensionally relaxed, for example, via heating and/or removing tension. For example, pre-stretched elastomeric substrates can be relaxed by releasing the tension holding the substrate in the stretched state. In the case of heat shrinkable substrates, the substrates may be placed, for example, in a heated oven or heated fluid until the desired reduction in dimension is achieved.

In some embodiments, the irradiated substrate has an original length (or width) and is dimensionally relaxed in length (or width) by at least 20 (in some embodiments, at least 25, 30, 40, 50, 60, 70, or even at least 80) percent of the original length (or width). Higher percent changes of original length (or width) upon dimensional relaxation typically produce greater extensions in the substrate after relaxation.

In some embodiments, in the range from 0.5% to 99.5% of the first major surface of the three-dimensional polymeric article comprises the first regions.

In some embodiments, the first and second regions each have an average thickness, and wherein the average thickness of the second regions is at least 1 micrometer (in some embodiments, at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or even at least 100 micrometers) greater than the average thickness of the first regions. The thickness in a given (first or second) region of the three-dimensional polymeric article is the shortest distance between a point on the first major surface to the second major surface of the three-dimensional polymeric article within the given region.

Embodiments of the three-dimensional polymeric article described herein are useful for providing a dual-sided, textured wrapping film such that greater grip is realized both on an item wrapped by the film and the wrapped item itself.

EXEMPLARY EMBODIMENTS 1A

A three-dimensional polymeric article having first and second opposed major surfaces, a base body having a first dimension, a second dimension perpendicular to the first dimension, and a thickness, wherein the thickness is orthogonal to the first and second dimensions, wherein the base body comprises a plurality of alternating, adjacent first and second polymeric regions along the first dimension, wherein the second dimensions of the first and second regions extend at least partially across the second dimensions, wherein the first regions have a first crosslink density, wherein the second regions have a second crosslink density, wherein the second crosslink density of the second regions are less (in some embodiments, at least 1% less, 2% less, 3% less, 4% less, 5% less, 10% less, 15% less, 20% less, 25% less, 30% less, 35% less, 40% less, 45% less, 50% less, 55% less, 60% less, 65% less, 70% less, 75% less, 80% less, 85% less, 90% less, 95% less, or even 100% less) than the first crosslink density of the first regions, wherein the first and second regions extend perpendicularly in two directions from a central plane in the base body parallel to the first and second dimensions of the polymeric article, and wherein the second regions extend in each of said two directions further than does the first regions.

2A

The three-dimensional polymeric article of Exemplary Embodiment 1A having in the range from 0.5% to 99.5% of the first major surface comprising the first regions.

3A

The three-dimensional polymeric article of any preceding A Exemplary Embodiment, wherein the first and second regions comprise a filler material (e.g., inorganic material).

4A

The three-dimensional polymeric article of any preceding A Exemplary Embodiment, wherein the first and second regions each have an average thickness, and wherein the average thickness of the second regions is at least 1 micrometer (in some embodiments, at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or even at least 100 micrometers) greater than the average thickness of the first regions (wherein the thickness in a given (first or second) region of the three-dimensional polymeric article is the shortest distance between a point on the first major surface to the second major surface of the three-dimensional polymeric article within the given region).

1B

A method of making the three-dimensional polymeric article, the method comprising:

providing an oriented, crosslinkable film having first and second opposed major surfaces,

irradiating (e.g., with e-beam, UV, x-ray, and/or gamma radiation) through at least a portion of the first major surface of the oriented, crosslinkable film to cause at least some portions under the first major surface to be irradiated and at least partially crosslink to provide first irradiated portions, wherein there remain after said irradiating at least second portions that are less irradiated than (which include zero irradiation) the first irradiated portions and, wherein the first irradiated portions have a lower shrink ratio than the second irradiated portions; and

dimensionally relaxing (e.g., via heating and/or via removing tension) the irradiated film.

2B

The method of Exemplary Embodiment 1B, wherein portions of the first major surface are masked to at least reduce exposure of the radiation through at least portions of the first major surface.

3B

The method of Exemplary Embodiment 1B or 2B that provides a three-dimensional polymeric article of any preceding A Exemplary Embodiment.

Advantages and embodiments of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. All parts and percentages are by weight unless otherwise indicated.

EXAMPLES Materials

Designation Description PO Heat Shrink Film Polyolefin (PO) heat shrink film, 25 micrometers, shrink ratio ~4.4:1, (25 micrometers) (obtained from Sealed Air, Elmwood Park, NJ, under trade designation “CRYOVAC D-955”) was laminated to a 3 mil (75 micrometer) polyethylene terephthalate (PET) film with a thin film of latex emulsion pressure sensitive adhesive (PSA) to form a multilayer film that is easier to handle. The PO heat shrink film layer was peeled away from the PSA/PET film prior to heating. PO Heat Shrink Film Polyolefin (PO) heat shrink film, 19 micrometers, shrink ratio ~4.4:1, (19 micrometer)s (obtained from Sealed Air, Elmwood Park, NJ, under trade designation “CRYOVAC D-955”). Circular Hole Array Perforated aluminum plate, 1/16″ (1.59 mm) thick, with hexagonal array Mask-I of circular holes 3/32″ (2.38 mm) diameter holes (obtained from Amazon.com, under trade designation “ASID: B004OR1A7C). Circular Hole Array Perforated aluminum plate, 1/16″ (1.59 mm) thick, with hexagonal array Mask-II of circular holes 3/16″ (4.76 mm) diameter holes (obtained from Amazon.com under trade designation “ASID: B004OR1A7C”).

Methods Method for Electron Beam Irradiation of Film Substrates

All electron beam (e-beam) irradiation was performed using an electron beam source (obtained under trade designation “ELECTROCURTAIN” from Energy Sciences, Inc. (ESI), Wilmington, Del.) running at 300 kV. The PO heat shrink film samples were taped with a polyester tape (obtained from 3M Company under trade designation “3M POLYESTER TAPE 8403”) onto a carrier web of PET film running at 18.9 ft./min. (5.76 m/min.) into the e-beam chamber. E-beam dose was controlled to deliver 2.5-40 Mrad in a single pass through the e-beam or cumulatively in multiple passes.

Method for Dimensionally Relaxing Substrates

Small pieces about 5 cm×5 cm (˜2 inches×˜2 inches) in size of the irradiated PO heat shrink film were cut with a pair of scissors and heated to convert to their “relaxed states.” More specifically, the heat shrink films were placed between two polytetrafluoroethylene (PTFE) mesh screens and placed in a preheated oven at 145° C. (air temperature) for about 45 to 120 seconds before rapidly removing and cooling to about 40° C. within 1 minute.

Method for Optical Microscopy

Optical images were obtained using a microscope (obtained under the trade designation “ZEISS STEMI 2000-C” from Allied High Tech Products, Inc., Rancho Dominguez, Calif.) with a digitizer (obtained under the trade designation “AXIOCAM ICC3” from Allied High Tech Products, Inc., Rancho Dominguez, Calif.) for digital image capture via a computer.

Method for Scanning Electron Microscopy

Images were obtained using a Scanning Electron Microscope (SEM) (obtained from JEOL Inc., Tokyo, Japan, under the trade designation “JEOL BENCH TOP SEM”). A 45° angle mount (obtained from Ted Pella, Inc., Redding, Calif., under trade designation “PELCO SEM CLIP 45/90° MOUNT” (#16357-20)) was used for mounting samples in the SEM. A small piece of conductive carbon tape (obtained from 3M Company, St. Paul, Minn., trade designation “3M TYPE 9712 XYZ AXIS ELECTRICALLY CONDUCTIVE DOUBLE SIDED TAPE”) was placed at the top of the 45° angle surface of the mount, and samples were mounted by affixing a small piece of the film/tube onto the carbon tape. If possible, the sample piece was situated as close to the top edge of the 45° angle surface as possible. A small amount of silver paint (obtained from Ted Pella, Inc., Redding, Calif., under trade designation “PELCO CONDUCTIVE LIQUID SILVER PAINT” (#16034)) was then applied to a small region of each sample piece, and extended to contact either the carbon tape, aluminum mount surface or both. After briefly allowing the paint to air dry at room temperature, the mounted sample assembly was placed into a sputter/etch unit (obtained from Denton Vacuum, Inc., Moorestown, N.J., under the trade designation “DENTON VACUUM DESK V”) and the chamber was evacuated to ˜0.04 Torr (5.33 Pa). Argon gas was then introduced into the sputtering chamber until the pressure stabilized at ˜0.06 Torr (8.00 Pa) before initiating the plasma and sputter coating gold onto the assembly for 90-120 seconds at ˜30 mA.

Cross-sectional images through the thickness of the films were obtained by orienting the sample 90 degrees relative to the beam. Thickness measurements were obtained from the image using the length measuring feature in the software (obtained under the trade designation “JCM-5000,” version 1.2.3 from JEOL Inc.). Thickness in a given (first or second) region of the film was measured as the shortest distance between a point on the first major surface to the second major surface of the film. For each region thickness, three separate locations within the region were measured and averaged.

Method for Measuring Swell Ratio

Swell Ratio was measured using ASTM D2765-01 (2006) (Test Method C), the disclosure of which is incorporated herein by reference. Samples of e-beam irradiated PO heat shrink film (19 micrometer) were immersed in 110° C. xylenes for 20 hours. Samples were weighed after the immersion period while wet and swollen, and again after drying.

Method for Calculating Crosslink Density

Crosslink density was calculated by dividing the density of the polymer film by the average molecular mass between crosslinks, M_(c). The average molecular mass between crosslinks, M_(c), was calculated using the Flory-Rehner equation (Equation 1).

$\begin{matrix} {\frac{1}{M_{c}} = {\frac{2}{M_{n}} - {\frac{\frac{v_{s}}{V_{1}}\left( {{\ln \left( {1 - v_{2}} \right)} + v_{2} + {\chi_{1}v_{2}^{2}}} \right)}{v_{2}^{1/3} - \frac{v_{2}}{2}}.}}} & {{Equation}\mspace{14mu} 1} \end{matrix}$

wherein, M_(c)=average molecular mass between crosslinks, M_(n)=number-average molecular mass of the un-crosslinked polymer, V₁=molar volume of the solvent, ν₂=polymer volume fraction in the equilibrium swollen gel, ν_(s)=specific volume of the polymer, and χ₁=polymer-solvent interaction parameter.

The polymer volume fraction in the equilibrium swollen gel, is the reciprocal of the swell ratio, Q. Under the conditions described in the section “Method for Measuring Swell Ratio”, Q, the molar volume of the solvent (xylenes), V₁, is 135.89 cm³/mole at 110° C., as calculated from the reciprocal of the density of xylenes at 110° C. The specific volume of the polymer, ν_(s), is the reciprocal of the density of the polymer. The density of PO heat shrink film is 0.7 g/cm³ (as reported in U.S. Pat. No. 6,340,532 B1 (Bormann et al.), Comparative Example 3, Table 4), and therefore ν_(s) is 1.084 cm³/g. The polymer-solvent interaction parameter, χ₁, used for low density polyethylene and xylenes at 120-140° C. is 0.28 and was obtained from Physical Properties of Polymers Handbook, AIP Press, New York, 1996, Chapter 14, Table 14.1. For the calculations herein, an estimated M_(n) value of 27,300 g/mol was used.

Method for Calculation of Critical Unit Compressive Stress

Upon dimensional relaxation, the masked (less irradiated) regions of the polymeric article have a higher shrink ratio and compress the unmasked (more irradiated) regions having a lower shrink ratio. The critical unit compressive stress, σ′ (i.e., buckling instability limit), is the stress limit above which an object will buckle and/or distort. The unmasked (exposed to e-beam radiation) regions in the Examples and Illustrative Examples are circular in form with a thickness (i.e., a circular plate). Equation 2 (below) was used to estimate the critical unit compressive stress, σ′ (i.e., buckling instability limit) of a circular plate being acted upon by a uniform radial edge compression as described in Young, W. C., Budynas, R. G., 2001, Roark's Formulas for Stress and Strain, 7th Ed., New York, McGraw-Hill Professional, p. 734, Table 15.2.

$\begin{matrix} {{\sigma^{\prime} = {K \cdot \frac{E}{1 - v^{2}} \cdot \left( \frac{t}{a} \right)^{2}}}{\begin{matrix} v & 0 & 0.1 & 0.2 & 0.3 & 0.4 \\ K & 0.282 & 0.306 & 0.328 & 0.350 & 0.370 \end{matrix}.}} & {{Equation}\mspace{14mu} 2} \end{matrix}$

wherein, K=Column effective length factor, E=Modulus of elasticity, ν=Poisson's ratio, a=Radius of circular plate, and t=Thickness of circular plate.

A Poisson's ratio (ν) of 0.46 (and therefore, K ˜0.370) was used (based on data for polyethylene as reported in [http://www.goodfellow.com/E/Polyethylene-High-density.html]) for PO heat shrink film (obtained under the trade designation “CRYOVAC D-955” from Sealed Air, Elmwood Park, N.J.).

The elastic modulus (E), for the heat shrink film (“CRYOVAC D-955”) was between 60,000 psi and 65,000 psi (413 MPa and 448 MPa, respectfully) for the longitudinal and transverse film directions, respectively, as reported in Technical Data Sheet for the “CRYOVAC D-955” PO heat shrink film.

The radius (a) and thickness (t) of the resulting exposed circular hole region was calculated assuming that no buckling in the hole (unmasked) region occurred after shrinking of the masked, irradiated PO heat shrink film by using the shrink ratio of the film in the hole (unmasked) regions. The shrink ratio of the hole (unmasked) regions was determined by measuring the length and width of an unmasked, irradiated film before and after irradiation and dimensional relaxation using a digital caliper (obtained under the trade designation “MODEL TRESNA EC16 SERIES, 111-101B,” 0.01 mm resolution, ±0.03 accuracy, from Guilin Guanglu Measuring Instruments Co., Ltd., Guilin, China). Thickness measurements were taken as the distance between the highest and lowest points in the overall film. Since, electron beam radiation can reduce the shrink ratio of PO heat shrink film depending on the dose as a result of the extent of crosslinking, shrink ratios of the PO heat shrink film were determined after exposing (as described above under “Method for Electron Beam Irradiation of Film Substrates”) the film to various doses of electron beam radiation as reported in Table 1A, below. Samples in Table 1A were 25-micrometer thick Polyolefin (PO) heat shrink films before shrinking and were placed in a preheated oven at 145° C. for 45 seconds. Calculated crosslink density values for PO heat shrink film irradiated at 0, 2.5, 5, 10, and 20 Mrad are summarized in Table 1B, below. Samples in Table 1B were 19-micrometer thick polyolefin (PO) heat shrink films before shrinking and were placed in a preheated oven at 145° C. for 120 seconds.

TABLE 1A Thickness Shrink after Dose/pass, # of Total Dose, Shrink Ratio Ratio shrinking, Mrads passes Mrads (width) (length) mm 0 0 0 5.07 4.55 0.57 5 1 5 3.47 3.30 0.30 10 1 10 2.78 2.87 0.18 20 1 20 2.13 2.03 0.10 20 2 40 1.66 1.71 0.06

TABLE 1B Crosslink Total Shrink Shrink density, Dose, Ratio Ratio Thickness after (×10⁻⁵) Mrads (width) (length) shrinking, mm Swell Ratio mol/cm³ 0 4.77 5.17 0.45 Undefined* 0*   2.5 3.58 4.21 0.30 422 6.76 5 3.29 3.40 0.21 75.1 6.88 10 2.53 2.72 0.14 21.3 7.89 20 2.24 2.39 0.11 12.5 9.76 *No gel remained after the immersion in hot xylenes, implying little to no (stable) crosslinking of the polymer is present in this sample under the test conditions.

Examples 1 and 2, Illustrative Examples A and B

Example (EX1), Example (EX2), Illustrative Example A (IE-A), and Illustrative Example B (IE-B) samples were prepared as described above in the “Method for Electron Beam Irradiation of Film Substrates” section. Table 2, below, summarizes the substrates, masks, and total dose for each sample in EX1, EX2, IE-A, and IE-B. Examples in Table 2 were 25-micrometer thick Polyolefin (PO) heat shrink films before shrinking and were placed in a preheated oven at 145° C. for 45 seconds.

TABLE 2 Number Total First Region Second Region Dose/Pass, of Dose, Thickness, Thickness, Example Substrate Mask Mrad Passes Mrad micrometers micrometers EX1 PO heat Circular 20 1 20 113 307 shrink Hole film Array Mask-I EX2 PO heat Circular 10 1 10 250 390 shrink Hole film Array Mask-II IE-A PO heat Circular 20 2 40 233 320 shrink Hole film Array Mask-I IE-B PO heat Circular 20 1 20 137 313 shrink Hole film Array Mask-II

Various optical images of EX1, EX2, IE-A, and IE-B are shown in FIGS. 3A-10B.

FIG. 3A is a perspective view scanning electron digital micrograph of Example 1.

FIG. 3B is an optical image of the top view of Example 1.

FIG. 4A is a cross-sectional view scanning electron digital micrograph of Example 1.

FIG. 4B is an optical image of the cross-sectional view of Example 1.

FIG. 5A is a perspective view scanning electron digital micrograph of Example 2.

FIG. 5B is an optical image of the top view of Example 2.

FIG. 6A is a cross-sectional view scanning electron digital micrograph of Example 2.

FIG. 6B is an optical image of the cross-sectional view of Example 2.

FIG. 7A is a top view scanning electron digital micrograph of Illustrative Example A.

FIG. 7B is an optical image of the top view of Illustrative Example A.

FIG. 8A is a cross-sectional view scanning electron digital micrograph of Illustrative Example A.

FIG. 8B is an optical image of the cross-sectional view of Illustrative Example A.

FIG. 9A is a perspective view scanning electron digital micrograph of Illustrative Example B.

FIG. 9B is an optical image of the top view of Illustrative Example B.

FIG. 10A is a cross-sectional view scanning electron digital micrograph of Illustrative Example B.

FIG. 10B is an optical image of the cross-sectional view of Illustrative Example B.

Table 3, below, summarizes the calculated expected values of radius (a), thickness (t), and critical unit compressive stress for the exposed circular hole regions in EX1, EX2, IE-A, and IE-B. The expected radius values (a) in Table 3 (below) were calculated by taking the product of hole radius and average shrink ratio values of width and length from Table 1 (above). The expected thickness values (t) in Table 3 (below) were taken from Table 1A, based on the corresponding Total Dose. The masked (less irradiated) regions were assumed to have a Total Dose near 0 Mrad.

TABLE 3 Total Critical Hole Dose, Unit Compressive Example Radius, mm Mrad T, mm a, mm Stress, MPa EX 1 1.190 20 0.1 0.56 6.47 EX 2 2.381 10 0.18 1.12 5.24 IE-A 1.190 40 0.06 0.56 2.33 IE-B 2.381 20 0.1 1.12 1.62

Based on the data from “CRYOVAC D-955” PO heat shrink film Technical Data Sheet, the shrink tension for the “CRYOVAC D-955” PO heat shrink film was ˜600 psi (4.14 MPa). Although not wanting to be bound by theory, comparing the calculated critical unit compressive stress and PO heat shrink film tension values in Table 3 (above), it appears there is a correlation as to whether exposed hole regions will buckle or remain planar during and after shrinking of the film. Although not wanting to be bound by theory, it appears that to obtain the structures of the Examples (e.g., as shown in FIGS. 1, 3A-6B), the critical unit compressive stress, σ′ (i.e., buckling instability limit), of any unmasked region should be greater than the compressive stress of the surrounding shrinking film region.

Foreseeable modifications and alterations of this disclosure will be apparent to those skilled in the art without departing from the scope and spirit of this invention. This invention should not be restricted to the embodiments that are set forth in this application for illustrative purposes. 

1. A three-dimensional polymeric article having first and second opposed major surfaces, a base body having a first dimension, a second dimension perpendicular to the first dimension, and a thickness, wherein the thickness is orthogonal to the first and second dimensions, wherein the base body comprises a plurality of alternating, adjacent first and second polymeric regions along the first dimension, wherein the second dimensions of the first and second regions extend at least partially across the second dimensions, wherein the first regions have a first crosslink density, wherein the second regions have a second crosslink density, wherein the second crosslink density of the second regions are less than the first crosslink density of the first regions, wherein the first and second regions extend perpendicularly in two directions from a central plane in the base body parallel to the first and second dimensions of the polymeric article, and wherein the second regions extend in each of said two directions further than does the first regions.
 2. The three-dimensional polymeric article of claim 1, wherein the second crosslink density of the second regions are less than 1 percent the first crosslink density of the first regions.
 3. The three-dimensional polymeric article of claim 1 having in the range from 0.5% to 99.5% of the first major surface comprising the first regions.
 4. The three-dimensional polymeric article of claim 1, wherein the first and second regions comprise a filler material.
 5. The three-dimensional polymeric article of claim 1, wherein the first and second regions each have an average thickness, and wherein the average thickness of the second regions is at least 1 micrometer greater than the average thickness of the first regions.
 6. A method of making the three-dimensional polymeric article of claim 1, the method comprising: providing an oriented, crosslinkable film having first and second opposed major surfaces, irradiating through at least a portion of the first major surface of the oriented, crosslinkable film to cause at least some portions under the first major surface to be irradiated and at least partially crosslink to provide first irradiated portions, wherein there remain after said irradiating at least second portions that are less irradiated than the first irradiated portions and, wherein the first irradiated portions have a lower shrink ratio than the second irradiated portions; and dimensionally relaxing the irradiated film.
 7. The method of claim 6, wherein irradiating is conducted via at least one of e-beam, UV, x-ray, or gamma radiation.
 8. The method of claim 6, wherein portions of the first major surface are masked to at least reduce exposure of the radiation to the first major surface. 